CN111330604A - Sodium borohydride hydrolysis hydrogen production catalyst, preparation method and application thereof - Google Patents
Sodium borohydride hydrolysis hydrogen production catalyst, preparation method and application thereof Download PDFInfo
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- CN111330604A CN111330604A CN202010183682.XA CN202010183682A CN111330604A CN 111330604 A CN111330604 A CN 111330604A CN 202010183682 A CN202010183682 A CN 202010183682A CN 111330604 A CN111330604 A CN 111330604A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 108
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 94
- 239000001257 hydrogen Substances 0.000 title claims abstract description 94
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 60
- 229910000033 sodium borohydride Inorganic materials 0.000 title claims abstract description 45
- 239000012279 sodium borohydride Substances 0.000 title claims abstract description 45
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 34
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229920005989 resin Polymers 0.000 claims abstract description 36
- 239000011347 resin Substances 0.000 claims abstract description 36
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 28
- JZTPOMIFAFKKSK-UHFFFAOYSA-N O-phosphonohydroxylamine Chemical compound NOP(O)(O)=O JZTPOMIFAFKKSK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920001429 chelating resin Polymers 0.000 claims abstract description 18
- 229910001429 cobalt ion Inorganic materials 0.000 claims abstract description 17
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 229910001453 nickel ion Inorganic materials 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims abstract description 11
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000013522 chelant Substances 0.000 claims abstract description 5
- 239000000446 fuel Substances 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- 229910017052 cobalt Inorganic materials 0.000 claims description 13
- 239000010941 cobalt Substances 0.000 claims description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 13
- 239000011973 solid acid Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000001630 malic acid Substances 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 235000011090 malic acid Nutrition 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 6
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 3
- 239000011574 phosphorus Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000008859 change Effects 0.000 abstract description 2
- 239000003446 ligand Substances 0.000 abstract description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- -1 nickel ion compound Chemical class 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000000498 ball milling Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical compound NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- 229910003266 NiCo Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- B01J35/23—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a sodium borohydride hydrolysis hydrogen production catalyst, a preparation method and application thereof, and belongs to the field of catalyst synthesis. According to the preparation method, the aminophosphoric acid chelating resin is used as a carrier to load Ni, Co or NiCoP compound active components, and nickel ions, cobalt ions or both enter holes in the aminophosphoric acid chelating resin through electrostatic attraction and group acting force and are strongly coordinated with a nitrogen-containing ligand so as to be distributed and fixed in the resin to form a stable resin-nickel ion, resin-cobalt ion or resin-cobalt ion/nickel ion compound; the composite is subjected to heat treatment, nickel ions, cobalt ions or a mixture of the nickel ions and the cobalt ions loaded on the amino phosphoric acid chelate resin and a phosphorus source form a NiP, CoP or NiCoP compound, and the NiP compound is carbonized to change a carbon carrier. The preparation method has the advantages of mild conditions, low cost, high yield, contribution to industrial production and no environmental pollution.
Description
Technical Field
The invention belongs to the field of catalyst synthesis, and particularly relates to a sodium borohydride hydrolysis hydrogen production catalyst, a preparation method and application thereof.
Background
In order to overcome the problems of energy shortage and environmental pollution in the future, the technology for utilizing hydrogen energy is increasingly important. Hydrogen energy is of great interest because of its storability, high efficiency, cleanliness, etc. The hydrogen fuel cell has wide application prospect in the fields of fixed power stations, electric vehicles, military special power supplies, movable power supplies and the like, but the fuel cell needs high-purity hydrogen, the conventional industrial hydrogen production process is complex, the storage safety is low, the energy consumption is high, and the requirement of large-scale production of the fuel cell cannot be met, so that the seeking of a method for preparing the high-purity hydrogen is the key for developing the portable power supply technology.
NaBH4Catalytic hydrolysis is a convenient, practical and novel hydrogen generation technology that can effectively prepare high-purity hydrogen. The hydrogen storage capacity can reach 10.8 wt%, the generation rate of hydrogen is easy to control, the purity of the prepared hydrogen is high, a purification process is not needed, and the catalyst can be circulated, so that the hydrogen is one of the best hydrogen sources of the proton exchange membrane fuel cell. This allows NaBH to be used4The hydrolysis hydrogen production technology has become a research hotspot which is concerned in recent years. In order to realize stable and efficient hydrogen release by sodium borohydride hydrolysis, the technical key is to find a catalyst which has low cost, simple and convenient preparation and excellent recycling performance.
At present, the sodium borohydride hydrolysis hydrogen production catalyst mainly comprises two types of noble metal-based and non-noble metal-based catalysts, researches show that the noble metal catalysts are mostly palladium-based and ruthenium-based catalysts (Guella G, Patton B, MiotelloA.J Phys Chemi C,2007,111(50): 18744-50; Akbayr S.S, Morkan S.int.J. hydrogen Energy 2014; 39: 9628-37; Chen Y, Liu Y.J. mater.Chem 2014; 2: 9193-9). the noble metal catalysts can effectively improve the hydrolysis hydrogen release rate of sodium borohydride to a certain extent, but the noble metals are expensive and have limited reserves, are difficult to be widely applied in practical production, therefore, in order to improve the catalytic rate of the catalysts, the non-noble metal catalysts are widely researched and applied in the field of sodium borohydride hydrolysis hydrogen production, wherein the catalytic effects of cobalt and nickel catalysts are all expressed in the forms of a binary catalyst, such as a catalyst, a catalyst.
Disclosure of Invention
The invention aims to overcome the defects that the existing sodium borohydride hydrolysis hydrogen production catalyst cobalt and nickel catalysts are easy to agglomerate, oxidize and fall off, and provides a sodium borohydride hydrolysis hydrogen production catalyst, a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
a preparation method of a sodium borohydride hydrolysis hydrogen production catalyst comprises the following steps:
1) dissolving a cobalt source, a nickel source or a nickel-cobalt mixture in water to form a solution A;
adding the aminophosphoric acid chelating resin into the solution A, and stirring for 8-24h to form a solution B;
2) and (3) taking the precipitate in the solution B, and heating the precipitate at 600-1100 ℃ for 1-5 h to obtain a NiP catalyst loaded on resin carbon, a CoP catalyst loaded on resin carbon or a NiCoP catalyst loaded on resin carbon.
Further, the nickel source in the step 1) is one or more of nickel chloride, nickel sulfate, nickel nitrate and nickel acetate;
the cobalt source in the step 1) is one or more of cobalt chloride, cobalt sulfate, cobalt nitrate and cobalt acetate.
Further, the mass ratio of the cobalt source compound or/and the nickel source compound to the amino phosphoric acid chelating resin in the solution A is (1-4): 2.
further, when the mixture of nickel and cobalt is used in the step 1), the mass ratio of nickel ions to cobalt ions in the solution a is (1:0.1) to (1: 10).
Further, the method also comprises a step 3), and the step 3) is as follows:
and uniformly mixing the NiP supported by the resin carbon, the CoP supported by the resin carbon or the NiCoP supported by the resin carbon with a solid acid ball mill to form the mixed catalyst of the NiP supported by the solid acid-resin carbon, the CoP supported by the solid acid-resin carbon or the NiCo supported by the solid acid-resin carbon.
Further, the solid acid is one or more of citric acid, oxalic acid, phosphoric acid and malic acid.
Further, the mass ratio of the resin carbon-supported NiP, the resin carbon-supported CoP or the resin carbon-supported NiCoP to the solid acid is 1: (0.1-10).
The sodium borohydride hydrolysis hydrogen production catalyst obtained by the preparation method of the invention.
The catalyst of the invention is used for catalyzing solid sodium borohydride to produce hydrogen.
Further, the method comprises the following steps:
mixing sodium borohydride and the catalyst uniformly to prepare fuel tablets;
the fuel pieces are placed into a hydrogen generator, water is pumped into the fuel pieces by a micro pump, and hydrogen is collected.
Compared with the prior art, the invention has the following beneficial effects:
the invention relates to a preparation method of a catalyst for hydrogen production by sodium borohydride hydrolysis, which utilizes aminophosphoric acid chelating resin as a carrier, wherein the aminophosphoric acid chelating resin has abundant and uniform holes, in a solution B, the aminophosphoric acid chelating resin is used as the carrier to load Ni, Co or NiCoP compound active components, nickel ions, cobalt ions or both enter the holes in the aminophosphoric acid chelating resin through electrostatic attraction and group acting force, the nickel ions and the cobalt ions are strongly coordinated with charged oxygen-containing or uncharged nitrogen-containing ligands, and the nickel ions and the cobalt ions or both are well distributed and fixed in the resin to form stable resin-nickel ions, resin-cobalt ions and resin-cobalt ions/nickel ion compounds; and (3) carrying out heat treatment on the composite, wherein the amino phosphoric acid chelating resin provides a phosphorus source during the heat treatment, and nickel ions, cobalt ions or a mixture of the nickel ions and the cobalt ions loaded on the amino phosphoric acid chelating resin and the phosphorus source form a NiP, CoP or NiCoP compound which is carbonized to change a carbon carrier. Thus obtaining the target products NiP/RC, CoP/RC or NiCoP/RC. The preparation method has mild conditions, low cost and high yield, is beneficial to industrial production and does not cause environmental pollution.
Further, the mass ratio of the cobalt source compound or/and the nickel source compound to the amino phosphoric acid chelating resin in the solution A is (1-4): 2, the catalyst has larger specific surface area, provides more attachment sites for the active components of the catalyst, can provide proper loading capacity for the active components of the catalyst, and also ensures that the active components of the catalyst can be effectively anchored on a carrier and are not easy to fall off and agglomerate.
Further, when the mixture of nickel and cobalt is obtained in the step 1), the mass ratio of nickel ions to cobalt ions in the solution a is 1: (0.1-10), the combination of the nickel element and the cobalt element can generate interaction and activity synergy, so that the composite catalyst has higher activity and stability compared with a single metal.
According to the catalyst for hydrogen production by hydrolysis of sodium borohydride, amino phosphoric acid chelating resin is subjected to heat treatment to form resin carbon, the abundant pore structure of the resin carbon is reserved, the resin carbon is used as a carrier to load Ni, Co or NiCo compound active components, and Ni ions, Co ions or both of the Ni ions and Co ions enter pores in the amino phosphoric acid chelating resin through electrostatic attraction and radical acting force to form stable resin-nickel ion, resin-cobalt ion and resin-cobalt ion/nickel ion compounds. After heat treatment, NiP, CoP or NiCoP composite nano particles are formed and uniformly distributed on the resin carbon carrier. In addition, the binding force between the active component and the carrier can ensure that catalyst particles can be uniformly loaded on the surface of the carrier, and the carrier can keep a specific shape, so that the stability of the catalyst is facilitated.
Furthermore, the solid acid mixture is used for catalyzing the hydrogen production reaction of the solid sodium borohydride, so that the rapid starting of the reaction can be realized, the solid acid is used as a catalyst for the hydrogen production of the sodium borohydride, an acidic environment is provided for the reaction in the hydrogen production of the sodium borohydride, and the hydrogen production reaction can be very rapid; however, when used alone, the hydrogen production per unit mass is still to be improved. Therefore, the prepared catalyst is mixed with solid acid, so that the reaction can be quickly started and the hydrogen production efficiency can be improved.
The invention relates to application of a catalyst for hydrogen production by sodium borohydride hydrolysis, wherein when the catalyst is used for catalyzing sodium borohydride to produce hydrogen, the whole reaction system is a solid phase. The system is not prepared into borohydride solution with lower concentration, and the system volume energy density of the fuel cell can be improved. In addition, compared with a borohydride liquid mixture, the solid-phase system is convenient to carry and move; the method also overcomes the influence of the dissolution of a by-product sodium metaborate in the solution on the reaction rate and the defects that the catalyst in the solution system is easy to inactivate and needs to be replaced regularly. The catalyst has the advantages of large active surface area, good stability, larger active contact area with solid sodium borohydride, stable existence and contribution to the hydrogen production reaction by sodium borohydride hydrolysis.
Drawings
FIG. 1 is a topographical view of the NiCoP/RC catalyst of example 1, wherein FIG. 1(a) is a TEM image of the NiCoP/RC catalyst and FIG. 1(b) is a particle size distribution plot of the NiCoP/RC catalyst;
FIG. 2 is an EDS test chart for the NiCoP/RC catalyst of example 1;
FIG. 3 is a graph showing the performance test of the NiCoP/RC-malic acid mixed catalyst and the NiCoP/RC catalyst of example 1, wherein FIG. 3(a) is a graph showing the variation of hydrogen production with time in the hydrolysis process of solid sodium borohydride with the NiCoP/RC malic acid mixed catalyst and the NiCoP/RC catalyst of example 1; FIG. 3(b) is a graph showing the variation of hydrogen production rate with time in the hydrogen production process by solid sodium borohydride hydrolysis catalyzed by the NiCoP/RC mixed catalyst and the NiCoP/RC catalyst of example 1;
RC is resin carbon formed after the amino phosphoric acid chelating resin is carbonized.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, shall fall within the scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below with reference to the accompanying drawings:
the preparation and catalytic performance of the catalyst of the present invention are further illustrated by the following specific examples.
Example 1
Preparation of NiCoP/RC-malic acid catalyst
First, 20g of an aminophosphonic acid chelate resin was ball-milled for 3 hours to be in a powder form. Then, nickel chloride and cobalt chloride were dissolved in ultrapure water, respectively, to prepare 0.15mol ∙ L-1The solution of (1); mixing 250mL of nickel chloride solution and 250mL of cobalt chloride solution to form a solution A; adding the amino phosphoric acid chelating resin subjected to ball milling into the solution A, and stirring at the speed of 750r/min for 24 hours; the resulting solution was then suction filtered under reduced pressure and washed with distilled water. Then, drying the obtained solid at 50 ℃ for 6h in vacuum; and calcining the mixture for 1h at 1000 ℃ in a tubular furnace under the protection of nitrogen in the calcining process, wherein the heating rate is 5 ℃/min, and thus obtaining the NiCoP/RC.
Mixing the NiCoP/RC prepared in the above step with malic acid in a mass ratio of 1:1, and carrying out ball milling for 3h to obtain the NiCoP/RC-malic acid mixed catalyst.
Then, 1g of sodium borohydride and 0.2g of the prepared catalyst are ground and mixed uniformly, and the mixture is pressed into fuel pieces with the diameter of 2cm by a hydraulic press for standby. The fuel tablet is put into a hydrogen generator, water is pumped into the generator by a micro pump, and after the water is contacted with the fuel tablet, the hydrogen is collected by adopting a drainage method.
In the catalytic solid sodium borohydride hydrolysis hydrogen production reaction, after reacting for 90min, the volume of 1876mL of hydrogen produced by using the NiCoP/RC-malic acid mixed catalyst is 1.34 times (1397mL) of the volume of hydrogen produced by using the NiCoP/RC catalyst, and is 3.16 times (593mL) of the volume of hydrogen produced by not using the catalyst. After reacting for 90min, the hydrogen production rate by using NiCoP/RC-malic acid mixed catalyst is 12 mL/min-1Is 1.5 times (8mL min) of the hydrogen production volume by using NiCoP/RC catalyst-1) 2 times the volume of hydrogen produced without using a catalyst (6 mL. min)-1)。
Referring to FIG. 1, FIG. 1(a) is a TEM test of NiCoP/RC of example 1, and it can be seen from FIG. 1(a) that the catalyst of example 1 is uniformly dispersed on the support with almost no agglomeration; as can be seen from the particle size distribution diagram of FIG. 1(b), the average particle size of the NiCoP/RC catalyst is about 1.88 nm.
Referring to fig. 2, fig. 2 is an EDS test chart of the NiCoP/RC catalyst of example 1, and it can be seen from fig. 2 that the composite catalyst of example 1 contains four elements of ni, co, p and c, further proving that NiCoP/RC can be successfully obtained by the preparation method of the present invention.
Referring to fig. 3, fig. 3(a) is a graph showing the variation of hydrogen production and time in the hydrogen production process by hydrolysis of solid sodium borohydride with the NiCoP/RC mixed catalyst and the NiCoP/RC catalyst of example 1, wherein the abscissa is the hydrogen production time, the ordinate is the hydrogen production amount, the hydrogen production amount of the catalyst is proportional to the time, and the hydrogen production amount of the catalyst increases with the time; at any time, when a NiCoP/RC-solid acid mixed catalyst is used, the hydrogen production is greater than that of a single NiCoP/RC catalyst, and greater than that when no catalyst is used. FIG. 3(b) is a graph showing the variation curve of hydrogen production rate and time in the process of hydrogen production by hydrolysis of solid sodium borohydride with the catalyst, the abscissa shows the hydrogen production time, and the ordinate shows the hydrogen production rate. This shows that the NiCoP/RC-solid acid mixed catalyst prepared by the present example can work for a long time, and the catalytic activity is still high and the service life is long after the work.
Example 2
Preparation of NiP/RC-citric acid catalyst
First, 20g of an aminophosphonic acid chelate resin was ball-milled for 3 hours to be in a powder form. Subsequently, nickel chloride was dissolved in ultrapure water to prepare 0.05 mol. L-1The solution of (1). Secondly, the amino phosphoric acid chelating resin after ball milling is added into 250mL of nickel chloride solution and stirred for 24 hours at the speed of 750 r/min. The resulting solution was then suction filtered under reduced pressure and washed with distilled water. After that, the resulting solid was dried under vacuum at 50 ℃ for 6 h. And calcining the mixture for 5 hours in a tubular furnace at the temperature of 600 ℃, wherein the temperature rise rate is 5 ℃/min under the protection of nitrogen in the calcining process, and the NiP/RC is obtained.
Mixing the NiP/RC prepared in the above step with citric acid in a mass ratio of 1:0.5, and carrying out ball milling for 3h to obtain the NiP/RC-citric acid mixed catalyst.
Then, 1g of sodium borohydride and 0.2g of the prepared catalyst are ground and mixed uniformly, and the mixture is pressed into fuel pieces with the diameter of 2cm by a hydraulic press for standby. The fuel tablet is put into a hydrogen generator, water is pumped into the generator by a micro pump, and after the water is contacted with the fuel tablet, the hydrogen is collected by adopting a drainage method.
After reacting for 90min, the volume of NiP/RC-citric acid produced hydrogen is 1560mL, which is 1.12 times (1397mL) the volume of NiCoP/RC catalyst produced hydrogen, and 2.63 times (593mL) the volume of NiCoP/RC catalyst produced hydrogen. The hydrogen production rate of the NiP/RC-malic acid mixed catalyst is 10.5 mL/min-1Is 1.31 times (8mL min) of the hydrogen production volume by using NiCoP/RC catalyst-1) 1.75 times (6 mL. min.) the volume of hydrogen produced without using a catalyst-1)。
Example 3
Preparation of CoP/RC-phosphoric acid catalyst
First, 20g of an aminophosphonic acid chelate resin was ball-milled for 3 hours to be in a powder form. Subsequently, cobalt nitrate was dissolved in ultrapure water to prepare 2.5 mol. L-1The solution of (1). Secondly, the amino phosphoric acid chelating resin after ball milling is added into 500mL cobalt nitrate solution and stirred for 24h at the speed of 750 r/min. The resulting solution was then suction filtered under reduced pressure and washed with distilled water. After that, the resulting solid was dried under vacuum at 50 ℃ for 6 h. And calcining the mixture for 3 hours at 1100 ℃ in a tubular furnace under the protection of nitrogen in the calcining process, wherein the heating rate is 10 ℃/min, and thus the CoP/RC is obtained.
And mixing the prepared CoP/RC and oxalic acid in a mass ratio of 1:10, and performing ball milling for 3 hours to obtain the CoP/RC-oxalic acid mixed catalyst.
Then, 1g of sodium borohydride and 0.2g of the prepared catalyst are ground and mixed uniformly, and the mixture is pressed into fuel pieces with the diameter of 2cm by a hydraulic press for standby. The fuel tablet is put into a hydrogen generator, water is pumped into the generator by a micro pump, and after the water is contacted with the fuel tablet, the hydrogen is collected by adopting a drainage method.
After the reaction for 90min, the hydrogen production volume of CoP/RC-oxalic acid is 1640mL, which is 1.17 times (1397mL) the hydrogen production volume using NiCoP/RC catalyst, and 2.76 times (593mL) the hydrogen production volume without catalyst. The hydrogen production rate of the NiP/RC-malic acid mixed catalyst is 11mL.min-1 which is 1.37 times (8 mL.min) of the hydrogen production volume of the NiCoP/RC catalyst-1) 1.83 times (6 mL. min.) the volume of hydrogen produced without using a catalyst-1). In conclusion, the NiCoP/RC-solid acid composite catalyst prepared by the invention has the advantages of low cost, mild preparation conditions, environmental friendliness and high activity, is beneficial to industrial production, does not cause environmental pollution, and is an ideal catalyst for solid sodium borohydride hydrolysis hydrogen production.
Example 4
Mixing the NiCoP/RC prepared in the example 1 with two solid acids of oxalic acid and phosphoric acid according to the mass ratio of 1:5, and carrying out ball milling for 3h to obtain the NiCoP/RC-oxalic acid and phosphoric acid mixed catalyst.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical solution according to the technical idea proposed by the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. A preparation method of a sodium borohydride hydrolysis hydrogen production catalyst is characterized by comprising the following steps:
1) dissolving a cobalt source, a nickel source or a nickel-cobalt mixture in water to form a solution A;
adding the aminophosphoric acid chelating resin into the solution A, and fully stirring to form a solution B;
2) and (3) taking the precipitate in the solution B, and heating the precipitate at 600-1100 ℃ for 1-5 h to obtain a NiP catalyst loaded on resin carbon, a CoP catalyst loaded on resin carbon or a NiCoP catalyst loaded on resin carbon.
2. The preparation method of the catalyst for hydrogen production by hydrolysis of sodium borohydride according to claim 1, wherein the nickel source in step 1) is one or more of nickel chloride, nickel sulfate, nickel nitrate and nickel acetate;
the cobalt source in the step 1) is one or more of cobalt chloride, cobalt sulfate, cobalt nitrate and cobalt acetate.
3. The preparation method of the catalyst for hydrogen production by hydrolysis of sodium borohydride according to claim 1, characterized in that the mass ratio of the cobalt source compound or/and the nickel source compound to the amino phosphoric acid chelate resin in the solution A is (1-4): 2.
4. the method for preparing the catalyst for hydrogen production by hydrolysis of sodium borohydride according to claim 1, wherein when the mixture of nickel and cobalt is used in step 1), the mass ratio of nickel ions to cobalt ions in the solution a is 1: (0.1-10).
5. The preparation method of the catalyst for hydrogen production by hydrolysis of sodium borohydride according to claim 1, 2, 3 or 4, characterized by further comprising step 3), wherein step 3) is:
the resin carbon supported NiP, resin carbon supported CoP or resin carbon supported NiCoP is mixed with a solid acid to form a solid acid-resin carbon supported NiP, solid acid-resin carbon supported CoP or solid acid-resin carbon supported NiCoP mixed catalyst.
6. The preparation method of the catalyst for hydrogen production by hydrolysis of sodium borohydride according to claim 5, wherein the solid acid is one or more of citric acid, oxalic acid, phosphoric acid and malic acid.
7. The preparation method of the catalyst for hydrogen production by hydrolysis of sodium borohydride, according to claim 5, is characterized in that the mass ratio of NiP supported by resin carbon, CoP supported by resin carbon or NiCoP supported by resin carbon to solid acid is 1 (0.1-10).
8. A catalyst for hydrogen production by hydrolysis of sodium borohydride obtained by the production method according to any one of claims 1 to 7.
9. The application of the catalyst for hydrogen production by hydrolysis of sodium borohydride according to claim 8, wherein the catalyst is used for hydrogen production by catalysis of solid sodium borohydride.
10. The application of the catalyst for hydrogen production by hydrolysis of sodium borohydride according to claim 9, is characterized by comprising the following steps:
mixing sodium borohydride and the catalyst uniformly to prepare fuel tablets;
the fuel pieces are placed into a hydrogen generator, water is pumped into the fuel pieces by a micro pump, and hydrogen is collected.
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